This review discusses the impact of alpha‐gallium oxide (α‐Ga2O3) on potential high‐power device applications. To date, there are high requirements for efficient high‐power delivery and low‐power loss device material in power industries. III‐VI oxide semiconductor family, α‐Ga2O3, is recognized as a promising, future power semiconductor material owing to its ultrawide bandgap of 5.3 eV, high breakdown field of 10 MV cm−1, and a large Baliga's figure of merit. A highly expected α‐Ga2O3 power semiconductor electronic device (Schottky barrier diode and field effect transistor) can perform better than conventional semiconductor materials Si, SiC, and GaN. However, there is a lack of research into using mist CVD to cultivate high‐quality α‐Ga2O3 for high‐power devices like FETs and SBDs. Currently, the mist CVD‐grown α‐Ga2O3 thin film power device is still in its early stages, and one of the main reasons for this is defects of the thin film, which impede material electron mobility. The purpose of writing this article is to provide an overview of the development of α‐Ga2O3 heteroepitaxial thin film by the mist CVD process for use in high‐power devices such as Schottky barrier diodes (SBD) and field effect transistors (MOSFET). 1. α‐Ga2O3 α‐Ga2O3. Furthermore, multiple viewpoints highlight the challenges and future trends toward device performance sustainability in a scientific society.